溶剂效应对NH、O和Se取代的2,1,3-苯并噻二唑衍生物光电性质影响的理论研究
|
摘要
采用理论计算方法研究了溶剂效应对杂原子NH、O和Se取代的2,1,3-苯并噻二唑衍生物电子性质和光谱性质的影响.结果表明,考虑溶剂效应后,NH取代对母体分子的电子性质和光谱性质的影响最明显.溶剂相和气相相比较,所研究分子的最高占据轨道和最低空轨道的能级都降低,能隙减小,最大吸收波长和最大发射波长都发生红移,并且振子强度增大,说明溶剂的加入有助于发光强度的提高.
The calculations predict electronic and optical properties upon the heteroatoms-substitution( NH,O,and Se) based on the 2,1,3-benzothiadiazole derivative considering solvent effect. The calculations showed that,NH substitution induced significant effect on the electronic and optical properties of the pristine molecule.Compared with that of in the gas phase,the solution effects induced the lowering in the HOMO and LUMO energy levels and the decreasing in the energy gap. The introduction of the solvent effects led to red shifts for all the maximum absorption and emission wavelength and the enhancement of the oscillator strength.
The calculations predict electronic and optical properties upon the heteroatoms-substitution( NH,O,and Se) based on the 2,1,3-benzothiadiazole derivative considering solvent effect. The calculations showed that,NH substitution induced significant effect on the electronic and optical properties of the pristine molecule.Compared with that of in the gas phase,the solution effects induced the lowering in the HOMO and LUMO energy levels and the decreasing in the energy gap. The introduction of the solvent effects led to red shifts for all the maximum absorption and emission wavelength and the enhancement of the oscillator strength.
引文
[1]胡波,董明明.给、吸电子取代基对2,1,3-苯并噻二唑衍生物的电子、光谱、电荷传输性质以及稳定性影响的理论研究[J].吉林师范大学学报(自然科学版),2011,32(3):24-27.
[2]胡波,刘腊梅,张浩.“CH”/N取代对BTD衍生物光电性质影响的理论研究[J].分子科学学报,2012,28(1):79-83.
[3]胡波,周凌云,靳瑞发.F原子取代对喹喔啉(quinoxaline)衍生物光电性质影响的理论研究[J].吉林师范大学学报(自然科学版),2012,33(2):12-14.
[4]胡波,王悦.环戊二噻吩中的硫原子被CH2、Si H2取代对化合物光电性质影响的理论研究[J].化学通报,2012,75(1):63-68.
[5]胡波,齐晓影.基于2,1,3-苯并噻二唑衍生物的有机发光材料的设计与性质的理论研究[J].化学研究与应用,2012,24(2):168-174.
[6](a)ROOTHAAN C C J.New developments in molecular orbital theory[J].Rev Mod Phys,1951,23(2):69-89.(b)POPLE J A,NESBET R K.Self-consistent orbitals for radicals[J].J Chem Phys,1954,22:571-578.(c)MCWEENY R,DIERCKSEN G.Self-consistent perturbation theory.II.Extension to open shells[J].J Chem Phys,1968,49:4852-4856.
[7]PARR R G,YANG W.Density functional theory of atoms and molecules[M].Oxford University Press:Oxford,1989.
[8](a)ERNZERHOF M,SCUSERIA G E.Assessment of the Perdew-Burke-Ernzerhof exchange-correlation functional[J].J Chem Phys,1999,110(11):5029-5036.(b)ADAMO C,BARONE V.Toward reliable density functional methods without adjustable parameters:the PBE0 model[J].J Chem Phys,1999,110(13):6158-6170.
[9]FORESMAN J B,HEAD-GORDON M,POPLE J A,et al.Toward a systematic molecular orbital theory for excited states[J].J Phys Chem,1992,96:135-149.
[10](a)STRATMANN R E,SCUSERIA G E,FRISCH M J.An efficient implementation of time-dependent density-functional theory for the calculation of excitation energies of large molecules[J].J Chem Phys,1998,109(19):8218-8224.(b)BAUERNSCHMITT R,AHLRICHS R.Treatment of electronic excitations within the adiabatic approximation of time dependent density functional theory[J].Chem Phys Lett,1996,256:454-464.(c)CASIDA M E,JAMORSKI C,CASIDA K C,et al.Molecular excitation energies to high-lying bound states from timedependent density-functional response theory:Characterization and correction of the time-dependent local density approximation ionization threshold[J].J Chem Phys,1998,108(11):4439-4449.
[11](a)HARIHARAN P C,POPLE J A.Accuracy of an equilibrium geometries by single determinant molecular-orbital theory[J].Mol Phys,1974,27(1):209-214.(b)GORDON M S.The isomers of silacyclopropane[J].Chem Phys Lett,1980,76:163-168.(c)FRISCH M J,POPLE J A,BINKLEY J S.Self-consistent molecular orbital methods 25.Supplementary functions for Gaussian basis sets[J].J Chem Phys,1984,80(7):3265-3269.
[12](a)MIERTU S,SCROCCO E,TOMASI J.Electrostatic interaction of a solute with a continuum.A direct utilizaion of AB initio molecular potentials for the prevision of solvent effects[J].Chem Phys,1981,55:117-129.(b)MIERTUS,TOMASI J.Approximate evaluations of the electrostatic free energy and internal energy changes in solution processes[J].Chem Phys,1982,65:239-245.(c)COSSI M,BARONE V,CAMMI R,et al.Ab initio study of solvated molecules:a new implementation of the polarizable continuum model[J].Chem Phys Lett,1996,255:327-335.
[13]FRISCH M J,TRUCKS G W,SCHLEGEL H B,et al.Gaussian 03,revision B.03;Gaussian,Inc.,Pittsburgh,PA,2003.
[2]胡波,刘腊梅,张浩.“CH”/N取代对BTD衍生物光电性质影响的理论研究[J].分子科学学报,2012,28(1):79-83.
[3]胡波,周凌云,靳瑞发.F原子取代对喹喔啉(quinoxaline)衍生物光电性质影响的理论研究[J].吉林师范大学学报(自然科学版),2012,33(2):12-14.
[4]胡波,王悦.环戊二噻吩中的硫原子被CH2、Si H2取代对化合物光电性质影响的理论研究[J].化学通报,2012,75(1):63-68.
[5]胡波,齐晓影.基于2,1,3-苯并噻二唑衍生物的有机发光材料的设计与性质的理论研究[J].化学研究与应用,2012,24(2):168-174.
[6](a)ROOTHAAN C C J.New developments in molecular orbital theory[J].Rev Mod Phys,1951,23(2):69-89.(b)POPLE J A,NESBET R K.Self-consistent orbitals for radicals[J].J Chem Phys,1954,22:571-578.(c)MCWEENY R,DIERCKSEN G.Self-consistent perturbation theory.II.Extension to open shells[J].J Chem Phys,1968,49:4852-4856.
[7]PARR R G,YANG W.Density functional theory of atoms and molecules[M].Oxford University Press:Oxford,1989.
[8](a)ERNZERHOF M,SCUSERIA G E.Assessment of the Perdew-Burke-Ernzerhof exchange-correlation functional[J].J Chem Phys,1999,110(11):5029-5036.(b)ADAMO C,BARONE V.Toward reliable density functional methods without adjustable parameters:the PBE0 model[J].J Chem Phys,1999,110(13):6158-6170.
[9]FORESMAN J B,HEAD-GORDON M,POPLE J A,et al.Toward a systematic molecular orbital theory for excited states[J].J Phys Chem,1992,96:135-149.
[10](a)STRATMANN R E,SCUSERIA G E,FRISCH M J.An efficient implementation of time-dependent density-functional theory for the calculation of excitation energies of large molecules[J].J Chem Phys,1998,109(19):8218-8224.(b)BAUERNSCHMITT R,AHLRICHS R.Treatment of electronic excitations within the adiabatic approximation of time dependent density functional theory[J].Chem Phys Lett,1996,256:454-464.(c)CASIDA M E,JAMORSKI C,CASIDA K C,et al.Molecular excitation energies to high-lying bound states from timedependent density-functional response theory:Characterization and correction of the time-dependent local density approximation ionization threshold[J].J Chem Phys,1998,108(11):4439-4449.
[11](a)HARIHARAN P C,POPLE J A.Accuracy of an equilibrium geometries by single determinant molecular-orbital theory[J].Mol Phys,1974,27(1):209-214.(b)GORDON M S.The isomers of silacyclopropane[J].Chem Phys Lett,1980,76:163-168.(c)FRISCH M J,POPLE J A,BINKLEY J S.Self-consistent molecular orbital methods 25.Supplementary functions for Gaussian basis sets[J].J Chem Phys,1984,80(7):3265-3269.
[12](a)MIERTU S,SCROCCO E,TOMASI J.Electrostatic interaction of a solute with a continuum.A direct utilizaion of AB initio molecular potentials for the prevision of solvent effects[J].Chem Phys,1981,55:117-129.(b)MIERTUS,TOMASI J.Approximate evaluations of the electrostatic free energy and internal energy changes in solution processes[J].Chem Phys,1982,65:239-245.(c)COSSI M,BARONE V,CAMMI R,et al.Ab initio study of solvated molecules:a new implementation of the polarizable continuum model[J].Chem Phys Lett,1996,255:327-335.
[13]FRISCH M J,TRUCKS G W,SCHLEGEL H B,et al.Gaussian 03,revision B.03;Gaussian,Inc.,Pittsburgh,PA,2003.